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Fuel
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h i g h l i g h t s
Thermal and catalytic pyrolysis of one non-edible oil seed Mahua was carried out.
525 C was the optimum temperature to produce maximum pyrolytic liquid.
Yield of pyrolytic oil was higher for catalytic pyrolysis than thermal pyrolysis.
CaO as catalyst increased the caloric value and decreased the viscosity.
The catalytic pyrolytic oil has closer fuel properties with that of diesel.
a r t i c l e
i n f o
Article history:
Received 7 August 2013
Received in revised form 2 September 2013
Accepted 2 September 2013
Available online 13 September 2013
Keywords:
Mahua seed
Thermal pyrolysis
Catalytic pyrolysis
Fuel properties
Composition
a b s t r a c t
In this work, the production and evaluation of fuel properties of pyrolytic oil from one non-edible oil seed
Mahua was reported. Both thermal and catalytic pyrolysis using CaO was carried out. The aim of the
study was to detect the optimum temperature to produce maximum pyrolytic oil and to increase the
quality of oil using catalyst. It was observed that thermal pyrolysis of Mahua seed at 525 C produced
maximum yield of liquid. Hence the inuence of catalyst was examined at the optimum temperature
(525 C) on liquid yield and its properties.
The catalytic effect of CaO, on Mahua seed pyrolysis at a feed to catalyst ratio of 2:1, 4:1 and 8:1 was
studied. The pyrolytic liquid collected was separated into two phases. The top phase (organic) was considered as oil phase where as the bottom phase as aqueous. Maximum yield of 40.71 wt.% of oil with better fuel properties was obtained as Mahua seed pyrolyzed in the presence of CaO at the ratio of 2:1. The
result conrmed that catalyst (CaO) not only increased the heating value (4143.15 MJ kg1), viscosity
(0.0330.018 Pa s) and cold ow properties but also altered the pH (4.868.58) signicantly when compared with thermal pyrolysis.
2013 Elsevier Ltd. All rights reserved.
1. Introduction
The fuel which does not originate from fossil fuel is termed as
alternative fuel. Alternative fuel is the advanced and future fuel derived from non-conventional sources of earth. Among various
alternative fuels, biofuel is gaining a lot of interest due to its various advantages over other alternative fuels. Biofuels can be solid,
liquid or gaseous fuel derived from biomass and hence it is CO2
neutral fuel. Owing to their renewability; biodegradability and
generating adequate quality exhaust gases, it is an approving option to be consumed as fuel [1]. The rapid growth of population
and industrialization decreases the forest level and as a result increases the percentage of CO2 level in the atmosphere. Deforestation and burning of fossil fuel causes more than 90% of global
warming [2]. Plantation is the only one approach which can be
Corresponding author. Tel.: +91 361 2582267; fax: +91 361 2582291.
E-mail address: kmohanty@iitg.ernet.in (K. Mohanty).
0016-2361/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.09.001
an obstacle for global warming. The production of fuel from biomass is accepted as an advance and future fuel.
Among various biofuels, pyrolytic oil derived from biomass
(commonly known as bio-oil) is also another alternative fuel of
interest. Verities of non-edible oils were traditionally used as lightening agents in various parts of the world since many decades. The
non-edible seeds are the main sources for this which contains
maximum quantity of oil and fats. Mahua (Madhuca indica) seed
is one of such oil containing seeds whose oil is being used for lightening as well as for the production of biodiesel [3]. Mahua trees are
vastly available in various parts of India as well as other countries.
It can grow in rainy area and all types of soils. Mahua seed holds
maximum 35% of oil and 16% of protein. During expelling at most
1520% of oil can be possible to extract whereas the rest remain in
the cake and used as cattle feed or to increase the fertility of soil.
Literatures reveal that pyrolysis is one of the suitable processes
to produce maximum 65% of oil from oil containing seeds [411].
The process pyrolysis means, heating materials at elevated
temperature in presence of very less amount of air or oxygen. During pyrolysis the higher molecular weight compounds such as
hydrocarbon, breaks to form lower molecular weight, short chain
hydrocarbons. The condensable liquid hydrocarbon is known as
pyrolytic oil. Pyrolysis of biomass yields three form of fuel such
as solid fuel which remains at the end of the process, condensable
volatiles as liquid fuel and the non-condensable gases as gaseous
fuel [5]. The quality and quantity of the pyrolytic oil depends on
the oil content and the composition of the feed stock. One of the
advantage of pyrolytic oil that it is easier to handle, store and
transport and can be a source of production of several chemicals
[6]. Literature reveals, the pyrolytic liquid produced from castor
seed separated into two layer such as oil and aqueous [4]. The caloric value and density of oil layer were very close to diesel. Maximum 64.5% of production of oil could be possible by thermal
pyrolysis of castor seed [4]. Linseed pyrolysis produced 57.7 wt.%
of liquid yield at 550 C where, [7] 44% yield was possible at
550 C from safower seed at a heating rate of 5 C min1 and
sweep gas (N2) ow rate 100 mL min1 [8] and maximum liquid
yield observed at 500 C during slow pyrolysis of pomegranate
seeds [9]. Duman et al. found maximum pyrolytic oil yield of
44 wt% at pyrolysis temperature of 500 C for both CWS and CSS
[10]. Catalytic pyrolysis of Pistacia khinjuk seed was carried out
with BP3189 and Criterion-424 as catalyst and a liquid yield of
66.5% and 69.2% was found for the two catalysts respectively.
The thermal pyrolysis yield for the same seed was only 57.6%.
The results conrmed that the use of catalyst increased the pyrolytic liquid yield both qualitatively and quantitatively [11].
A lot of work has been done on thermal pyrolysis of different
seeds but a few works were reported on catalytic pyrolysis of
seeds. This paper reports the thermal and catalytic pyrolysis of Mahua seed. Thermal pyrolysis was carried out to study the maximum
yield of oil at minimum temperature. The effect of catalyst (CaO) in
three different feed to catalyst ratio (2:1, 4:1 and 8:1) were studied
to determine the optimum ratio for maximum liquid yield with
better fuel properties. The aim of selecting this particular catalyst
was that literature reveals catalytic cracking with CaO reduces
the tar yield as well as emission of CO2. CaO absorbs CO2 and form
CaCO3 and results in zero emission of CO2 during pyrolysis. The
reactions involved are provided below [1215]:
1
1
1
373
Catalytic pyrolysis experiments were conducted at the optimum temperature determined by thermal pyrolysis, at different
feed to catalyst ratio (2:1, 4:1 and 8:1) in the same stainless steel
batch reactor as mentioned in the earlier section. Calcium oxide
(CaO) was purchased from Loba Chemie, India, (P) Ltd. and used
as catalyst (BET surface area: 37 m2 gm1, MW: 56.0074 g mol1).
The catalyst was used directly without any treatment and the yield
was calculated as described in the above section. The product obtained from thermal and catalytic pyrolysis was compared on the
basis of yield, physical and chemical properties. Later on the process was optimized and the ratio of feed to catalyst for maximum
production of pyrolytic oil was determined.
100
92%
88%
80
74%
60
n
er
sio
40
nv
Co
the liquid samples were performed using Excalibur Bio-Rad spectrophotometer (Model FTS 3500 GX) attached with DRS without
using KBr. One drop of liquid sample was loaded in the sample
holder and the IR spectra were collected at scan rate of 40 with a
step size of 4 cm1 within the range of 4004000 cm1.
20
13%
M
ax
im
um
2.5.1. Viscosity
The viscosity of the pyrolytic oil was determined at 25 C and
50 rpm using rheometer (HAKEE Rheostress 1). Cone and plate
type (Meas. Cup Z 43 (Series 1) and Plate PP 35 Ti, D = 35 mm)
geometry was used to determine the viscosity where temperature
was controlled accurately 0.05 C by HAAKE DC-50 temperature
controller. A series of rheological data collected and the average
was accepted as viscosity of the oil.
374
0
0
100
200
300
400
o
Temp. ( C)
Fig. 1. TG analysis of Mahua seed.
500
600
375
60
55
50
Yield (wt.%)
Table 1
Composition of Mahua seed: Proximate and ultimate analysis.
Proximate analysis
Wt. (%)
Ultimate analysis
Wt. (%)
Moisture content
Volatile matter
Ash content
Fixed carbon
5.65
91.76
1.49
1.1
Carbon (C)
Hydrogen (H)
Nitrogen (N)
Oxygen (O)
Sulfur (S)
55.87
7.94
2.74
33.201
0.249
Extractive Content
Hexane extractives (%)
56.75
0.41
40
35
30
25
20
500
525
550
575
600
Temperature ( C)
Fig. 2. Thermal pyrolysis yield of Mahua seed with respect to temperature.
81
Conversion (%)
45
80
79
78
77
500
520
540
560
580
600
Temp. ( C)
Fig. 3. Conversion of Mahua seed with respect to temperature.
in aqueous yield was observed after 550 C. The increase in aqueous yield was due to the formation of more water in pyrolytic liquid at higher temperature which gets separated as bottom layer.
376
60
55
Conditions
50
45
40
Thermal
2:1 CaO
4:1 CaO
8:1 CaO
35
25
Aqueous phase
4.86
8.58
8.42
8.33
4.81
8.63
8.72
8.72
20
10
2:1
4:1
8:1
97
0.70
Oil phase
Aqueous phase
96
0.60
95
0.55
94
0.50
93
0.45
0.40
92
0.35
91
0.30
90
Thermal
2:1 CaO
4:1 CaO
8:1 CaO
Oil phase
30
15
0.65
pH
CaO
R COOH ! CO2 RH
Table 3
Inuence of catalyst on distillation temperature of pyrolytic oil.
Distillation temperature, C
Feed to catalyst ratio
% Distillation
10
20
30
40
50
60
70
80
90
Thermal
177
230
265
288
306
320
333
348
386
2:1 CaO
108
137
168
195
232
262
290
320
365
4:1 CaO
161
202
230
255
271
291
314
339
377
8:1 CaO
131
181
209
234
255
275
296
321
366
377
Viscosity
0.035
Viscosity (Pa s)
0.030
0.025
0.020
0.015
0.010
Thermal
2:1 CaO
4:1 CaO
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
-0.5
-1.0
-1.5
-2.0
-2.5
-3.0
-3.5
2.53
Diesel
Thermal
2:1 CaO
4:1 CaO
8:1 CaO
3.96
11.30 Cooling
2.97
2.53
17.21
13.89
6.73
26.63
6.85
10.86
-9.34
Heating
-30
8:1 CaO
-3.46
10.43
-1.88
-20
-10
24.86
10.09
8.97
10
20
30
Temp. C
revealed that lower the feed to catalytic ratio lower is the caloric
value. The highest caloric value (43.15 MJ kg1) was obtained
from the pyrolysis of Mahua seed with CaO in the ratio of 2:1
which was closer to the caloric value of diesel fuel (45 MJ kg1).
Catalytic pyrolysis increased the caloric value of pyrolytic oil than
that of the thermal pyrolytic oil (from 41 to 43.15 MJ kg1). The increase in caloric value may be due to the decrease in acid content
and oxygen content of the pyrolysis oil as well as formation of
more volatile compounds which is discussed in the above section.
CaO helps to decrease the oxygen content of pyrolytic oil by the
formation of water [1215,38]
Table 4
Caloric value of thermal and catalytic pyrolytic oil and diesel.
Pyrolytic oil
Thermal
2:1 CaO
4:1 CaO
8:1 CaO
Diesel
41
43.15
42.39
41.85
45
Lower
temperature
melting peak
(C)
Minimum high
melting peak
temp. (C)
Onset
freeze
temp. (C)
P2
Maximum high
freezing peak
temp. P1 (C)
Diesel
Thermal
2:1 CaO
4:1 CaO
8:1 CaO
3.46
1.88
9.33
8.97
24.86
10.09
10.43
10.86
6.73
26.63
12.89
11.30
6.85
3.96
17.21
2.97
2.53
2.53
378
observed in this region. The observed result showed that increasing feed to catalyst ratio lowered the low temperature melting
peak. The comparison of DSC analysis of diesel with thermal and
catalytic pyrolytic oil conrmed that the lower temperature melting temperature decreased from 24.86 to 10.09 by catalytic pyrolysis with CaO in the ratio of 2:1 which was very closer to diesel
(8.97). Similarly, during cooling period all the pyrolytic oil and diesel endowed with a single peak. The onset temperature of each
peak was regarded as onset crystallization temperature where
the peak point denoted to the maximum high freezing peak temperature (P1) of the oils. At the onset temperature the oils started
to freeze and at the peak temperature (P2) it completely freezes
and was considered as pour point of that oil which lies in between
the peak temperature and onset temperature. The P1 and P2 was
lower for the catalytic pyrolytic oil obtained at lower feed to catalyst ratio than thermal. The use of CaO catalyst decreased the pour
point of pyrolytic oil which was conrmed from this analysis and
the detail about cold ow temperature of diesel, thermal and catalytic pyrolytic oil can be observed from Table 5. The catalytic
pyrolytic oil offered the lower onset crystallization temperature
(2.53 C) which is comparable with diesel (3.96 C).
90
90
85
85
80
80
75
75
70
70
65
65
60
60
55
55
50
50
45
4500 4000 3500 3000 2500 2000 1500 1000 500
45
4500 4000 3500 3000 2500 2000 1500 1000 500
cm-1
cm-1
100
100
4:1 CaO
95
90
90
85
85
80
80
75
75
70
70
65
65
60
60
55
55
50
50
45
4500 4000 3500 3000 2500 2000 1500 1000 500
8:1 CaO
95
%T
%T
2:1 CaO
95
%T
%T
100
Thermal
95
600500
900670
12501350
1225950
15101450
17251750
17001725
20001800
2922
35703200
36403530
100
Wave No.
45
4500 4000 3500 3000 2500 2000 1500 1000 500
cm-1
Fig. 8. FTIR Comparison between thermal and catalytic pyrolytic oil.
cm-1
379
Peak area,
%
Name of Compound
Molecular
weight
RT
Peak area,
%
Name of Compound
Molecular
weight
8.63
8.80
8.96
8.21
1.653
0.820
0.412
0.544
116
193
281
355
12.80
12.96
14.70
14.85
0.462
0.306
0.490
0.289
Cyclopropane
Nonane
1-Decene
Decane
126
128
140
142
10.47
10.74
10.92
12.47
12.79
12.95
13.05
14.70
14.85
16.47
16.59
18.21
5.352
1.097
1.171
0.967
0.870
0.822
0.672
0.658
0.833
0.635
0.537
0.658
Fumaric acid
Pyrimidine, 4,6-dichloro-5-nitroAcetamide, N-(4-bromophenyl)-2,2-dichloroBenzamide, N-(2-iodo-4-methylphenyl)-3uoroNitric acid, ethyl ester
Pterin-6-carboxylic acid
Phenol, 2,4-dichloro-6-nitro3-Pyridinecarboxaldehyde
2,4-Dichloro-6-nitrophenol
1-Amino-2-ethylhexane
Benzamide, N,N-didecyl-3-methoxyHentriacontane
Pyridine, 3-(triuoromethyl)N-(4-triuoromethylbenzoyl)-, dodecyl ester
Acetic acid butoxyethanol ester
Benzamide, N,N-diundecyl-2-uoro-
91
207
207
107
207
129
431
436
147
429
320
447
16.47
16.64
16.60
18.10
18.22
19.71
19.611
21.022
21.117
22.34
22.43
22.93
0.656
0.349
0.349
0.676
0.446
0.965
0.840
2.073
1.208
1.739
3.072
0.524
168
168
212
168
184
184
186
210
212
228
166
132
19.71
21.02
21.10
22.33
22.42
23.58
0.745
1.028
1.001
0.938
2.055
1.281
434
443
198
446
213
436
23.51
23.58
23.66
24.75
24.81
24.82
0.625
2.031
1.424
2.212
6.783
7.343
1-Undecene
Cyclopropane, nonylDodecane, 2,6,11-trimethylCyclododecane
Decane, 2,6,8-trimethylTridecane
1-Dodecanol
1-Pentadecene
Pentadecane
N-heptadecanol-1
4-Cyclohexyl-1-butanol
Benzene, 4-ethenyl-1,2dimethyl4-Hexadecylester
Cyclohexadecane
Octadecane
N-tridecyl ester
Oxacyclohexadecan-2-one
Hexadecane, 2,6,10,14tetramethyl-
23.65
2.493
226
24.64
5.813
24.81
2.359
224
224
254
296
240
282
283
240
[26]. Peak noticed in the range between 3570 and 3200 cm1 may
be due to alcohol and other hydroxyl compounds (normally AOH
stretch). The presence of AOH group in the pyrolytic oil also may
be due to the presence of water content. It can be observed that
the peak of AOH group increased with decrease in feed to catalytic
ratio. Aromatic ring (aryl) group and aromatic combination bond
was obtained at 20001800 cm1. The presence of functional
groups and their respective wave number is listed in Table 6. The
comparison between thermal and catalytic pyrolytic oil clearly conrmed that the presence of CAH stretch of an aliphatic compound
of methyl and methylene group compounds in the range of 2850
3000 cm1 were increased in catalytic pyrolytic oil. This conrmed
that catalytic pyrolysis increased the concentration of methylene
group compounds than thermal pyrolytic oil.
3.4.7. GCMS analysis
The results of physical properties conrmed that catalytic pyrolysis of Mahua seed with CaO in the ratio of 2:1 offered good quality of oil compared to thermal pyrolytic oil. The composition was
determined by GCMS analysis and presented in Table 7. The comparison of GCMS results between thermal and catalytic pyrolytic
oil conrmed that catalytic pyrolysis generated lower molecular
hydrocarbons than thermal pyrolysis. No such acid, amide and pyridine compounds were detected in catalytic pyrolytic oil. The presence of acid compounds made the thermal pyrolytic oil acidic in
nature. Catalytic pyrolysis of Mahua seed with CaO catalyst produced short chain hydrocarbon compounds, where as thermal
pyrolytic oil resulted in long chain hydrocarbons. Several benzene
and its derivative compounds were noticed in thermal pyrolytic oil
whereas the catalytic pyrolytic oil contained very less amount of
benzene compounds. Thermal pyrolytic oil was a mixture of several compounds with higher area% of acid and ester compounds
whereas catalytic pyrolytic oil contained higher decane and its
derivatives.
4. Conclusions
In this work, Mahua seed was used to produce pyrolytic oil by
thermal and thermo-catalytic process and compared. The optimum
temperature for maximum production of total pyrolytic liquid was
525 C as observed from thermal pyrolysis of Mahua seed. The
pyrolytic liquid product was separated into oil and aqueous phase
where the oil phase holds good fuel properties. Catalytic pyrolysis
conrmed that CaO in the ratio of 2:1 (feed to catalyst) produced
34.64% of oil which was higher than thermal pyrolytic yield. The
water analysis concluded that pyrolytic oil contains less than 1%
of water. Use of CaO catalyst decreased the viscosity, distillation
temperature of the pyrolytic oil with increase in caloric value.
The pH was completely altered from acidic to basic with the use
of the catalyst CaO. Comparison of GCMS analysis of thermal
and catalytic pyrolytic oils conrmed that Mahua catalytic pyrolytic oil contains short chain hydrocarbon compounds such as decane and its derivatives where as thermal pyrolytic oil contains long
chain hydrocarbons.
From this study it was concluded that non-edible oil seed such
as Mahua can be used as a suitable feed stock for pyrolysis and the
pyrolytic oil can be used as fuel oil. The catalytic pyrolysis of Mahua seed conrmed that the presence of catalyst increased the fuel
quality, however, the amount of catalyst required to achieve this
was high. In this work only CaO was used as it has the ability to
capture CO2, however more study using different catalysts needs
to be done to nd out the best catalyst which will improve the fuel
quality with a much less amount of catalyst.
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